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US8680224B2 - Formaldehyde-free protein-containing binder compositions - Google Patents

Formaldehyde-free protein-containing binder compositions Download PDF

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Publication number
US8680224B2
US8680224B2 US12/697,968 US69796810A US8680224B2 US 8680224 B2 US8680224 B2 US 8680224B2 US 69796810 A US69796810 A US 69796810A US 8680224 B2 US8680224 B2 US 8680224B2
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Prior art keywords
binder composition
protein
binder
crosslinking
soy
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US12/697,968
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US20110189479A1 (en
Inventor
Mingfu Zhang
Kiarash Alavi Shooshtari
Jawed Asrar
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Johns Manville
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Johns Manville
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Assigned to JOHNS MANVILLE reassignment JOHNS MANVILLE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ASRAR, JAWED, SHOOSHTARI, KIARASH ALAVI, ZHANG, MINGFU
Priority to EP11000367.0A priority patent/EP2354205B1/en
Priority to CN201110037554.5A priority patent/CN102153988B/zh
Priority to US13/113,551 priority patent/US8809477B2/en
Publication of US20110189479A1 publication Critical patent/US20110189479A1/en
Priority to US13/296,768 priority patent/US8937025B2/en
Priority to US14/168,458 priority patent/US9587103B2/en
Publication of US8680224B2 publication Critical patent/US8680224B2/en
Application granted granted Critical
Priority to US14/334,787 priority patent/US9493617B2/en
Priority to US14/565,984 priority patent/US9683085B2/en
Priority to US15/280,824 priority patent/US10087350B2/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/06—Copolymers with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H99/00—Subject matter not provided for in other groups of this subclass, e.g. flours, kernels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J189/00—Adhesives based on proteins; Adhesives based on derivatives thereof
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2389/00—Characterised by the use of proteins; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00—Compositions of proteins; Compositions of derivatives thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/253—Cellulosic [e.g., wood, paper, cork, rayon, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2926—Coated or impregnated inorganic fiber fabric
    • Y10T442/2992—Coated or impregnated glass fiber fabric

Definitions

  • Thermoset binders for composite fiber products such as fiberglass insulation are moving away from traditional formaldehyde-based compositions.
  • Formaldehyde is considered a probable human carcinogen, as well as an irritant and allergen, and its use is increasingly restricted in building products, textiles, upholstery, and other materials.
  • binder compositions have been developed that do not use formaldehyde or decompose to generate formaldehyde.
  • formaldehyde-free binder compositions rely on esterification reactions between carboxylic acid groups in polycarboxy polymers and hydroxyl groups in alcohols. Water is the main byproduct of these covalently crosslinked esters, which makes these binders more environmentally benign, as compared to traditional formaldehyde-based binders.
  • these formaldehyde-free binder compositions also make extensive use of non-renewable, petroleum-based ingredients. Thus, there is a need for formaldehyde-free binder compositions that rely less on petroleum-based ingredients.
  • Protein As an abundant and renewable material, protein has great potential to be an alternative to petroleum-based binders. Proteins are already used extensively as a component of adhesives for various substrates. However, many types of protein-containing adhesives have poor gluing strength and water resistance. Thus, there is a need to improve the bonding strength and water resistance of protein-containing binder compositions to levels that are similar to or better than those of conventional, petroleum-based binder compositions.
  • One-part binder compositions are described that may include one or more proteins that actively crosslink with other binder constituents to provide a rigid thermoset binder.
  • the binder compositions are formaldehyde-free, and incorporate renewable materials like proteins from animal and vegetable sources (e.g., soy flour) that reduce or even eliminate the need for petroleum-based binder ingredients.
  • the components of the binder compositions may be selected to increase the pot life and reusability of pre-cured binder solutions without compromising on the quality of the cured binder product.
  • the binder compositions may include one-part compositions that can be cured without the addition of another compound. However, additional compounds such as a cure catalyst may optionally be added to accelerate the rate of curing or some other function. In addition, changes in temperature and/or other external conditions may be effected to cure the binder composition and produce a final product containing the cured binder.
  • additional compounds such as a cure catalyst may optionally be added to accelerate the rate of curing or some other function.
  • changes in temperature and/or other external conditions may be effected to cure the binder composition and produce a final product containing the cured binder.
  • Exemplary binder compositions may include at least three components that are all capable of forming covalent bonds with each other. These components may include at least one protein and a crosslinking combination of two or more crosslinking compounds.
  • the crosslinking compounds may include a first crosslinking compound (e.g., a polymer compound) and a second crosslinking compound (e.g., a crosslinking agent) that are individually crosslinkable with each other and with the protein.
  • the binder composition may include a protein, polymer compound and crosslinking agent that all have functional groups capable of forming covalent bonds with each other.
  • the protein may include hydroxyl and carboxyl groups that can form covalent bonds with complementary carboxyl and hydroxyl groups on the polymer compound and crosslinking agent.
  • the polymer compound and crosslinking agent are selected with complementary functional groups to form covalent bonds with each other (e.g., a polycarboxy polymer and hydroxyl-group containing crosslinking agent such as an amino alcohol).
  • a polycarboxy polymer and hydroxyl-group containing crosslinking agent such as an amino alcohol
  • the covalent bonding density in the cured binder may be higher than in binders where only two components form such bonds.
  • the increased covalent bond density in a binder system with three or more covalently bonding compounds may also allow the selection of more stable compounds for a one-part binder composition.
  • proteins, polymer compounds, and/or crosslinking agents may be selected that undergo covalent crosslinking reactions at a slower rate (e.g., a reaction rate that is about zero) under ambient conditions (e.g., room temperature), thereby extending the pot life (a.k.a. shelf life) of the one-part binder composition.
  • the stability of the individual compounds may be selected to give the one-part binder composition a pot life about 1 month or more.
  • Embodiments of the invention include one-part thermoset binder compositions that may include a protein and a crosslinking combination of two or more crosslinking compounds.
  • the crosslinking combination may include a first crosslinking compound and a second crosslinking compound, where the first and second crosslinking compounds are individually crosslinkable with each other and with the protein.
  • One specific, non-limiting example of the present binder compositions includes a polymer compound; a crosslinking agent crosslinkable with the polymer compound; and a protein that is crosslinkable with both the polymer compound and the crosslinking agent.
  • the protein may include soy protein which may, for example, be sourced from soy flour.
  • Embodiments of the invention may further include fiber products.
  • the fiber products may include inorganic or organic fibers (or both) and a cured thermoset binder prepared from a one-part binder solution.
  • the binder solution may include a protein and a crosslinking combination of two or more crosslinking compounds, where the protein and crosslinking compounds are all crosslinkable with each other.
  • Embodiments of the invention may still further include methods of making a fiber product.
  • the methods may include the steps of providing fibers that may be organic fibers or inorganic fibers, and applying a one-part binder solution to the fibers.
  • the one-part binder solution may include a protein and a crosslinking combination of two or more crosslinking compounds, where the protein and crosslinking compounds are all crosslinkable with each other.
  • the methods may further include reusing an unused portion of the one-part binder solution in a subsequent application of the one-part binder solution to the same fibers or a different group of fibers.
  • FIG. 1 is a graph of dogbone composite tensile tests for a selection of binder compositions described in the Examples below.
  • One-part binder compositions are described that include renewable materials such as proteins in combination with two or more other binder components.
  • Examples include one-part binder compositions made from at least one protein and a crosslinking combination of two or more crosslinking compounds, where the protein and crosslinking compounds are all crosslinkable with each other.
  • crosslinkable refers to the ability of two compounds to form covalent bonds with each other, although other type of bonds may also be formed between the compounds.
  • the one-part binder composition may optionally include additional components such as cure catalysts.
  • Binder solutions made from the present binder compositions may be applied to a substrate such as inorganic and/or organic fibers and cured to make a composite of the thermoset binder and substrate such as a building material (e.g., fiberglass insulation). These materials do not off-gas formaldehyde during their production and use, or decompose to contaminate factories, buildings, homes, and other areas with formaldehyde.
  • the binder compositions may at least partially substitute renewable compounds (e.g., proteins) for non-renewable compounds such as petroleum-based compounds.
  • Exemplary binder compositions may include compositions containing at least one protein and a crosslinking combination of two or more crosslinking compounds, where the protein and crosslinking compounds are all crosslinkable with each other.
  • the proteins used in the binder compositions may include vegetable and/or animal proteins. These proteins may be readily available from a renewable source. Examples of proteins that may be used in the binder compositions include soy protein, wheat protein, corn protein, whey, albumin, keratin, gelatin, collagen, gluten, casein, among other kinds of proteins.
  • the proteins may be used in an unmodified, un-denatured state (i.e., native proteins).
  • the proteins may be modified and/or denatured using physical, chemical, or enzymatic methods that cause changes to the primary, secondary, tertiary, and/or quaternary structures of the proteins. These methods may include denaturing the proteins to change their secondary, tertiary and quaternary structures, and chemically or enzymatically breaking down the protein molecules into smaller fragments. They may also include modifying the pendant moieties of the protein, such as adding additional carboxyl and/or hydroxyl groups to the protein molecules.
  • Soy protein in the form of a soy flour, soy protein concentrate, soy protein isolate, and/or soy polymer, among other forms of soy protein.
  • Soy flour may be produced by grinding soybeans into a powder. Soy flour may retain the natural oils and other compounds from the soybeans, or may be defatted to produce flour with higher protein content (e.g., about 50 wt % protein or more). Soy protein concentrate contains about 70 wt % soy protein and is made by removing water soluble carbohydrates from defatted soy flour.
  • Soy protein isolate is a highly refined, purified form of soy protein with the protein content of about 90 wt. % or more. The isolates may be made from defatted soy flour that has most non-protein soybean components removed (e.g., fats, carbohydrates, etc.).
  • Soy polymers may include soy proteins that have been chemically modified to impart a variety of functionalities to protein molecules.
  • the soy protein may be denatured/modified to unfold protein molecules in the dispersion.
  • the functionalities of protein molecules e.g., carboxyl, hydroxyl, and amine
  • protein denaturation and modification methods include, but not limited to, heat treatment, treatment with chaotropic agents (e.g., urea, guanidinium chloride, and lithium perchlorate), acids, bases, metal salts, alcohols, detergents, thiols, sulfites, and mixtures thereof.
  • the soy protein may also be modified to reduce the viscosity of soy protein dispersion, therefore reducing the viscosity of protein-based thermoset binder compositions.
  • methods of reducing the viscosity of soy protein dispersion include, but not limited to, hydrolyzing protein using enzymes or alkalis, cleaving disulfide bonds in protein by thiols or sulfites.
  • the viscosity of soy protein dispersion may be reduced by the treatment with sodium bisulfite.
  • the relative amount of protein to add can vary depending on other binder components used, the processing conditions, and the type of end product being made, among other considerations.
  • Embodiments have the concentration of the protein (as a percentage weight of the binder composition) ranging from about 5% to about 95%; about 10% to about 90%; about 25% to about 80%; about 20% to about 60%; about 20% to about 50%; about 30% to about 70%; etc.
  • Soy protein such as soy flour may be dispersed or dissolved in water.
  • Other binder ingredients such as the crosslinking compounds (e.g., monomer and polymer compounds, crosslinking agents, etc.), are mixed with the aqueous soy protein dispersion or solution to form the final binder composition that is applied to the fibrous products.
  • the crosslinking compounds e.g., monomer and polymer compounds, crosslinking agents, etc.
  • the crosslinkable combination of crosslinking compounds may include monomeric compounds and/or polymer compounds, among other classes of crosslinking compounds. These crosslinking compounds may be selected to have complementary functional groups that can react to form covalent bonds.
  • one crosslinking compound may be a carboxyl-containing polycarboxy polymer, while a second crosslinking compound may be crosslinking agent that includes hydroxyl groups that react to form covalent bonds with the carboxyl groups.
  • the polymer compound may have reactive hydroxyl groups and the crosslinking agent may have reactive carboxyl groups that react to form covalent bonds.
  • carboxyl-containing polymer compounds include polycarboxy homopolymers and/or copolymers prepared from ethylenically unsaturated carboxylic acids including, but not limited to, acrylic acid, methacrylic acid, butenedioic acid (i.e., maleic acid and/or fumaric acid), methyl maleic acid, itaconic acid, and crotonic acid, among other carboxylic acids.
  • the polycarboxy polymer may also be prepared from ethylenically unsaturated acid anhydrides including, but not limited to, maleic anhydride, acrylic anhydride, methacrylic anhydride, itaconic anhydride, among other acid anhydrides.
  • the polycarboxy polymer of the present invention may be a copolymer of one or more of the aforementioned unsaturated carboxylic acids or acid anhydrides and one or more vinyl compounds including, but not limited to, styrenes, acrylates, methacrylates, acrylonitriles, methacrylonitriles, among other compounds. More specific examples of the polycarboxy polymer may include copolymers of styrene and maleic anhydride, and its derivatives including its reaction products with ammonia and/or amines. For example, the polycarboxy polymer may be the polyamic acid formed by the reaction between the copolymer of styrene and maleic anhydride and ammonia.
  • the polymer compound may be a solution polymer that helps make a rigid thermoplastic binder when cured.
  • the polymer compound is an emulsion polymer
  • the final binder compositions are usually less rigid (i.e., more flexible) at room temperature.
  • Crosslinking agents may include compounds containing at least two reactive functional groups including, but not limited to, hydroxyl, carboxyl, amine, aldehydes, isocyanate, and epoxide, among other functional groups.
  • Examples of crosslinking agents may include polyols, alkanol amines, polycarboxylic acids, polyamines, and other types of compounds with at least two functional groups that can undergo crosslinking of with other binder ingredients, such as proteins and polymer compounds.
  • polyols may include glycerol, ethylene glycol, propylene glycol, diethylene glycol, and triethylene glycol, among other polyols.
  • alkanol amines may include ethanolamine, diethanolamine, and triethanolamine, among other alkanol amines.
  • polycarboxylic acids may include malonic acid, succinic acid, glutaric acid, citric acid, propane-1,2,3-tricarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, among other polycarboxylic acids.
  • polyamines may include ethylene diamine, hexane diamine, and triethylene diamine, among other polyamines.
  • epoxies may include bisphenol-A based epoxies, aliphatic epoxies, epoxidized oils, among other epoxy compounds.
  • the crosslinking agent may react with both the polymer compound and the protein.
  • the crosslinking agent may be a polyol that is capable of reacting with not only the protein (e.g., soy protein) but also the polycarboxy polymer.
  • the binder compositions may include three components binders made from a single protein and a two-compound crosslinking combination.
  • binder compositions may include a plurality of proteins and compounds that make up the crosslinking combination (e.g., a plurality of polymer compounds, and/or crosslinking agents).
  • crosslinking combination e.g., a plurality of polymer compounds, and/or crosslinking agents.
  • two or more types of one component may be combined with a single species of each of the other components.
  • two or more type of two of the components may be combined with a single species of a third component.
  • two or more types of all three components may be present in the binder composition.
  • the binder compositions may also optionally include a cure catalyst.
  • cure catalysts may include phosphorous-containing compounds such as phosphorous oxyacids and their salts.
  • the cure catalyst may be an alkali metal hypophosphite salt like sodium hypophosphite (SHP).
  • SHP sodium hypophosphite
  • the binder compositions may also optionally include extenders.
  • extenders may include starch, lignin, rosin, among other extenders.
  • the binder compositions may also optionally contain pH adjustment agents.
  • the present binder compositions and solution may include one or more bases that maintain the pH at about 7 or more, about 8 or more, about 9 or more, about 9.5 or more, about 10 or more, about 10.5 or more, etc.
  • the protein in the binder composition may be actively crosslinkable with the members of the crosslinking combination.
  • the protein may be treated to expose the reactive moieties on polypeptide chains of the proteins (e.g., hydroxyl groups, carboxyl groups, amino groups, thiol groups) for crosslinking reactions.
  • the hydroxyl-containing amino acid moiety on protein chains e.g., serine, tyrosine, threonine
  • a carboxyl-containing amino acid moiety e.g., aspartic acid, glutamic acid
  • the present binder compositions may also exclude materials that have deleterious effects on the cured binder.
  • the binder compositions may have decreased levels of reducing sugars (or no reducing sugars at all) to reduce or eliminate Maillard browning that results from the reaction of these sugars at elevated temperatures.
  • Some binder compositions made from renewable materials can contain substantial levels of reducing sugars and other carbohydrates that produce a brown or black color in the cured binder. As a result, products made with these binder compositions are difficult or impossible to dye.
  • binder compositions include compositions where the concentration of reducing sugars is decreased to a point where discoloration effects from Maillard browning are negligible.
  • the fully cured binders may have a white or off-white appearance that allows them to be easily dyed during or after the curing process.
  • the present binder compositions may be used in methods of making fiber products.
  • the methods may include applying a solution of the binder composition to fibers and curing the binder composition on the fibers to form the fiber product.
  • the binder solution may be spray coated, spin coated, curtain coated, knife coated, or dip coated onto fibers.
  • the binder and substrate may be heated to cure the binder composition and form a composite of cured binder and fibers that make up the fiber product.
  • the binder solution may be formed to have a viscosity in range that permits the efficient application of the solution to the fibers.
  • the viscosity may be about 1 centipoises to about 1000 centipoises when the binder solution is at room temperature.
  • the viscosity of the liquid binder applied to the substrate may slow down the application process both at the release point for the binder as well as the rate of mixing and coverage of the binder on the substrate.
  • Solutions and dispersions of many types of protein, including some types of soy protein in aqueous solutions have generally high viscosities.
  • the present protein-containing binder compositions may include proteins with a relatively low viscosity when dissolved/dispersed in the liquid binder. These may include soy proteins that are modified to lower the viscosity of soy protein dispersion.
  • the amalgam of liquid binder and substrate undergoes curing.
  • the protein, polymer compound, and crosslinking agent may form covalently crosslinked bonds among each other to convert the amalgam into a thermoset composite.
  • the amalgam may be subjected to an elevated temperature (e.g., up to 300° C.) to facilitate crosslinking in the binder.
  • the peak curing temperature may depend on the specific formulation of the protein-containing binder composition, the substrate, and whether a cure catalyst is used.
  • the cured material typically includes about 0.5 wt % to about 50 wt % thermoset binder composition (e.g., about 1 wt. % to about 10 wt. %) with the substrate representing most of the remaining weight.
  • the binder composition may be a stable one-part composition that can be recycled during the application to the fibers and/or between applications on fibers.
  • an unused portion of the binder solution that, for example, passes through the fibers may be captured and sent back to the supply of binder solution applied to the fibers.
  • the unused portion of the binder solution may be purified or otherwise treated before returning to the supply.
  • the reuse of the binder solution may not only reduce the amount of solution used, it may also reduce the amount of waste materials that must be treated and discarded.
  • recycling unused binder solution requires that the solution remain stable for two or more application cycles.
  • two-part binder compositions that mix separated and highly reactive components immediately before their application will cure too rapidly to be recycled.
  • One-part binder compositions may also be unsuitable if they don't have a sufficient pot life to remain relatively unreacted prior to use and during recycling.
  • the present binder compositions include one-part binder compositions that are stable enough to be appropriate for binder solution recycling.
  • the present binder compositions may be added to fibers to produce composite fiber products.
  • the fibers may include organic fibers and/or inorganic fibers.
  • the fibers may include polymer fibers and/or glass fibers, among other types of fibers.
  • the fibers may be arranged as an insulation batt, woven mat, non-woven mat, or spunbond product, among other types of fiber substrate.
  • the present binder compositions may be used in fiber products to make insulation and fiber-reinforced composites, among other products.
  • the products may include fibers (e.g., organic and/or inorganic fibers) contained in a cured thermoset binder prepared from a one-part binder solution of a polymer compound, crosslinking agent that is crosslinkable with the polymer compound, and protein crosslinkable with both the polymer compound and crosslinking agent.
  • the fibers may include glass fibers, carbon fibers, and organic polymer fibers, among other types of fibers.
  • the combination of the binder composition and glass fibers may be used to make fiberglass insulation products.
  • the binder may be applied and cured to form printed circuit boards, battery separators, filter stock, and reinforcement scrim, among other articles.
  • the binder compositions may be formulated to impart a particular color to the fiber product when cured. For example, the concentration of reducing sugars in the binder compositions may be lowered to give the fiber product a white or off-white color when cured. Alternatively, a dye may be added to binder composition before, during, or after the curing stage to impart a particular color to the final fiber product (e.g., red, pink, orange, yellow, green, blue, indigo, violet, among may other colors).
  • a dye may be added to binder composition before, during, or after the curing stage to impart a particular color to the final fiber product (e.g., red, pink, orange, yellow, green, blue, indigo, violet, among may other colors).
  • defatted soy flour Prolia 200/90, Cargill
  • 50 grams of defatted soy flour (Prolia 200/90, Cargill) is dispersed in 200 ml of DI water at room temperature.
  • 0.5 grams of sodium bisulfite is then added to the soy flour dispersion.
  • the viscosity of the soy flour dispersion drops shortly after the addition of the sodium bisulfite.
  • the final soy flour dispersion has a solids concentration of 18.9% by oven method (drying at 125° C. for 2 hours).
  • defatted soy flour Prolia 200/90, Cargill
  • 50 grams of defatted soy flour (Prolia 200/90, Cargill) is dispersed in 200 ml of DI water at room temperature.
  • 0.5 grams of sodium bisulfite is then added to the soy flour dispersion.
  • the pH of the dispersion is adjusted to 11 using an ammonium hydroxide solution (25-30%).
  • the final soy flour dispersion has a solids concentration of 17.5% by oven method.
  • SMAc-TEA a copolymer of styrene and maleic anhydride having a molecular weight of approximately 2,000 and an acid number of 480.
  • SMAc-TEA a copolymer of styrene and maleic anhydride having a molecular weight of approximately 2,000 and an acid number of 480.
  • SMAc-TEA a copolymer of styrene and maleic anhydride
  • Example 8 To 79.4 grams of the soy flour dispersion of Example 1 is added with stirring 23.6 grams of the polyamic acid resin of Example 3, and 22 grams of water to achieve a total solids of 20% and a weight ratio between soy flour and SMAc-TEA of 60/40. The final binder composition is then used for dogbone composite tensile test as described below in Example 8.
  • Example 8 To 85.7 grams of the soy flour dispersion of Example 2 is added with stirring 23.6 grams of polyamic acid resin of Example 3 and 15.7 grams of water to achieve a total solids of 20% and a weight ratio between soy flour and SMAc-TEA of 60/40. The final binder composition is then used for dogbone composite tensile test as described below in Example 8.
  • Example 8 To 57.1 grams of the soy flour dispersion of Example 2 is added with stirring 35.4 grams of polyamic acid resin of Example 3 and 32.5 grams of water to achieve a total solids of 20% and a weight ratio between soy flour and SMAc-TEA of 40/60. The final binder composition was then used for dogbone composite tensile test as described below in Example 8.
  • Example 8 To 28.6 grams of the soy flour dispersion of Example 2 is added with stirring 47.2 grams of polyamic acid resin of Example 3 and 49.2 grams of water to achieve a total solids of 20% and a weight ratio between soy flour and SMAc-TEA of 20/80. The final binder composition is then used for dogbone composite tensile test, which is described below in Example 8.
  • Binder solutions are prepared from the five binder compositions by adding 5%, by weight, of sodium hypophosphite monohydrate and 1%, by weight, of aminosilane (Silquest A-1100). The binder solutions are mixed with glass beads to achieve a binder content of 2.4% for each composite of binder and glass beads. The composites are then pressed in molds of dogbone shape to form test samples. The molded samples are then dried and cured in an oven at 204° C. for 20 minutes.
  • FIG. 1 shows the tensile strength results for the five binder compositions described in Examples 3-7 before and after humid aging.
  • “SF” stands for “soy flour”.
  • the data shown in FIG. 1 represent the average of nine dogbone specimens for each sample and the error represents the standard deviation.
  • the tensile tests show that the binder compositions with soy flour that is not ammonia-modified yield a lower tensile strength, as compared to the binder composition without soy flour (e.g., SMAc-TEA). Significant increase in tensile strength was observed when soy flour was ammonia-modified. As shown in FIG. 1 , all binder compositions containing ammonia-modified soy flour show higher tensile strength than the binder composition without soy flour (e.g., SMAc-TEA). The humid-aging retention of tensile strength of all the binder compositions containing ammonia-modified soy flour is very high (>95%), indicating the high moisture resistance of the protein-based binder compositions of the present invention.

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CN201110037554.5A CN102153988B (zh) 2010-02-01 2011-01-31 不含甲醛的含蛋白质粘结剂组合物
US13/113,551 US8809477B2 (en) 2010-02-01 2011-05-23 Formaldehyde-free protein-containing binder compositions
US13/296,768 US8937025B2 (en) 2010-02-01 2011-11-15 Formaldehyde-free protein-containing binders for spunbond products
US14/168,458 US9587103B2 (en) 2010-02-01 2014-01-30 Formaldehyde-free protein-containing binder compositions
US14/334,787 US9493617B2 (en) 2010-02-01 2014-07-18 Formaldehyde-free protein-containing binder compositions
US14/565,984 US9683085B2 (en) 2010-02-01 2014-12-10 Formaldehyde-free protein-containing binders for spunbond products
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US20150031259A1 (en) 2015-01-29

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